Anti-fouling paint for ship&#39;s bottom and structures under sea water

ABSTRACT

AN ANTI-FOULING PAINT FOR SHIP&#39;&#39;S BOTTOM AND STRUCTURES UNDER SEA WATER COMPRISES AN EFFECTIVE AMOUNT FOR CONTROLLING SEA ORGANISM OF A TIN COMPOUND HAVING THE GENERAL FORMULA   R3-SN-O-CO-R&#39;&#39;-CO-O-SN-R3   WHEREIN R IS AN ALKYL OR PHENYL RADICAL AND R&#39;&#39; IS A HALOGENATED ETHYLENE OR A HALOGENATED PHENYLENE RADICAL, AND A COATING FILM FORMING MATERIAL.

US. Cl. 260-15 AF 11 Claims ABSTRACT OF THE DISCLOSURE An anti-foulingpaint for ships bottom and structures under sea water comprises aneffective amount for controlling sea organisms of a tin compound havingthe general formula 0 B38110 yJ-IV-E O S11R3 wherein R is an alkyl or aphenyl radical and R is a halogenated ethylene or a halogenatedphenylene radical, and a coating film forming material.

This is a continuation application Ser. No. 64,958, filed Aug. 19, 1970,now abandoned.

The present invention relates to an anti-fouling paint for ships bottomand structures under sea water comprising an effective amount of a tincompound having the general formula 0 o aasno'll-n-llosims wherein R isan alkyl or a phenyl radical and R is a halogenated ethylene or ahalogenated phenylene radical as an active ingredient and a coating filmforming material and further to a method for controlling sea organismsdeposited on the ships bottom and structures under sea water with thesame paint.

A commonly used paint for ships bottom is composed of three paints,i.e., anti-corrosive paint, anti-fouling paint and boot-top paint.

The anti-corrosive paint is used for preventing rust, the anti-foulingpaint is used to prevent depositing of foul and the boot-top paintisused for both said purposes. Therefore, the anti-corrosive paint must beadhered to a surface of a steel plate, form a coated film having anexcellent brine resistance and have a good adhesivity to theanti-fouling paint or the boot-top paint to be applied thereon. In thecase of vinyl series anti-corrosive paint, a wash primer consistingmainly of vinyl butyral resin is previously applied on the steel platein order to improve an adhesion of said paint to the steel plate andthen the paint is applied thereon. The anti-fouling paint aims toprevent depositing of sea organisms, for example, injurious animals,such as Balanus, Serpulids, Bryozoa, Gunicates; injurious plants, suchas Ultra pertusa, En teremorpha, etc., on the ships bottom and in thiscase the active ingredient contained in the paint is gradually dissolvedin sea water and prevents approaching and depositing of the seaorganisms to the ships bottom.

The present invention uses a tin compound as the active ingredient.

Heretofore, heavy metal compounds, such as copper suboxide, mercuryoxide, etc., have been used as the active ingredient. However, saidcompounds are often used in the form of oxide, so that they react with avarnish component contained in the paint during the storage and areusually unstable. Furthermore, mercury oxide cannot be used for thevinyl series anti-corrosive paint.

3,832,190 Patented Aug. 27, 1974 Moreover, when a conventionalwell-known organotin compound, for example, bis(trialkyltin) oxide ismixed with a coating film forming material, the resulting coated film isdifflcultly dried, blisters are liable to be formed and the storagestability is poor. Furthermore, trialkyltin halide, dialkyltin oxide andthe like have problems in the activity, storage stability, etc. Inaddition, bis(trialkyltin) fumarate is poor in the effect for preventingseaweeds which influence highly a speed of a ship.

The effective period of these known anti-fouling paints for ships bottomis about one year. Recently, a prolongation of a painting cycle has beendemanded strongly in the shipping industry and it is considerablydesired to produce the anti-fouling paint having an effective period ofmore than one year.

The active ingredients according to the present invention areparticularly effective to seaweeds, maintain the anti-fouling activityfor a long period and require no repair of the coated film for twoyears.

The active ingredients according to the present invention are listed,for example, as follows:

Compound 1. Bis (tri-isopropyltin meso-dibromosuccinate 0 O (lso-CsHmsnOfl CHI-011 0Sn(iso-C H1) m.p.: 1567 C. Compound 2.Bis(tridsopropyltin)meso-dichlorosucciuate O 0 (ho-0 11035110 y CH-CHJllOSn (-0 11 m.p.: 181 C. Compound 3.Bis(tri-n-propyltin)meso-dlchlorosuccinate 0 0 (11- C 3H7)3SDO g C H CHa 0 811(11- C3H7):

mp. 147-7 C. Compound 4. Bis(tri-n-butyltin)meso-dibromosuccinateCompound 5. Bis tri-n-butyltin)meso-dichlorosuccinate ll 11 (n-Cdib): SHO O CH-CHC O Sn(n--C4Ho)a m.p. 1313 C.

Compound 6. Bis(triphenyltin)meso-dibromosuccinate 0 0 3) MQ) 1'3. l. a

m.p.: 6 C. Compound 7. Bis(tri-n-butyltin)monochloromalate m.p.: 94-7 C.Compound 8. Bis(triphenyltin)monochloromalate o 0 (Q) snoa.. a..tos. a n3 Compound 9. Bis(tri-n-butyltin)tetrachloroterephtlialate O1 01 f l Theanti-fouling paint for ships bottom and structures under sea water ofthe present invention containing these compounds as the activeingredient can prevent satisfactorily depositing of the sea organisms,such as shell-fishes, seaweeds, etc., on the ships bottom even afterimmersed in sea for months, and particularly, shows an excellent effectto prevent the depositing of seaweeds which cause a reduction of a speedof ships at sea.

Furthermore, the compounds according to the present invention are verysmaller in bad odor and lower in toxicity than the conventionalorganotin compounds, e.g. tributyltin oxide, and further have nostimulation to a mucous membrane and they can be easily handled.

According to the present invention, these compounds are obtained pyreacting bis(tri-alkyl or phenyl-tin) oxide with organic acids.

These compounds may be mixed with a coating film forming material in awell-known convenient manner.

As a coating film forming material, use may be made of usual oily orsynthetic resin vehicles and also pigments are not limited. As a methodfor the production of antifouling paint, the active ingredient iscompounded in such an amount of 4.5 to 25% by weight and the resultingmixture is thoroughly pulverized and kneaded.

The present invention will be explained with respect to the followingPreparation Examples and Experimental Examples.

Preparation Example 1 Oily paint (blue colour):

Percent Compound 1 Titanium white 10 Cyanine Blue 1 Barium sulfate 7Talc 6 Aluminium stearate l Rosin Boiled oil 10 Solvent naphtha 20 Total100 Preparation Example 2 Vinyl chloride paint (red colour):

Percent Compound 4 20 Red oxide 15 Talc 10 Barium sulfate 7 Aluminiumstearate l Rosin 12 Chlorinated rubber 6 Diphenyl chloride 4 Solventnaphtha 25 Total 100 Experimental Example 1 (a) Test method Test platescoated with the anti-fouling paint for ships bottom of PreparationExample 1 were immersed in sea for two years. In each plate, there wasno deposit of sea organisms other than fur and the anti-fouling activitywas very high. Furthermore, the coated film did not form blisters andmaintained a good normal condition.

fialjj b) Results After one year Ultra pertusa, Entere- Compound tomorpha be tested Bryozoa Balanus Serpulids After two years Compound 4..N o deposit" N o deposit" No deposit No deposit. ControlA No deposit"Control A: Bis(tributyltin) tumarate. 4 N OTE: slightly deposited;considerably deposited.

Exeprimental Example 2 (a) Testmethod (1) Paint to be tested: Compounds1 to 9 of organotin compounds according to the present invention andcopper suboxide conventionally used were compounded in the mixing ratioas shown in Preparation Example 1, respectively.

(2) Manufacture of test plate: A polished steel plate of 300 x x 1 mm,was coated with the paint prepared in the above item (1) by means of abrush according to the following painting manner.

(3) Painting manner:

Times Wash primer 1 Anti-corrosive paint 2 Anti-fouling paint of thepresent invention or antifouling paint containing copper suboxide 2 (4)immersing method: The above-mentioned test plate was immersed in a depthof 1.5 m. of sea.

The test plate immersed in the sea was taken out at a constant interval,and the area of the sea organisms deposited thereon was measured toobtain a result as shown in the following table.

(b) Results Months It Compound:

Copper suboxide. N oil-treated 13 whole surface of the test plate; 0=NoNorE.5=Deposit on the deposit.

wherein R is a straight chain alkyl or a phenyl radical and R is ahalogenated ethylene or a halogenated phenylene radical to the shipsbottom and structures under sea water.

2. The method as claimed in claim 1, wherein said tin compound isbis(tri-isopropyltin)meso-dibrornosuccinate.

3. The method as claimed in claim 1, wherein said tin compound isbis(tri-isopropyltin)meso-dichlorosuccinate.

4. The method as claimed in claim 1, wherein said tin compound isbis(tri-n-propyltin)meso-dichlorosuccinate.

5. The method as claimed in claim 1, herein said tin compound isbis(tri-n-butyltin)meso-dibromosuccinate.

6. The method as claimed in claim 1, wherein said tin compound isbis(tri-n-butyltin)meso-dichlorosuccinate.

7. The method as claimed in claim 1, wherein said tin compound isbis(triphenyltin)meso-dibromosuccinate.

8. The method as claimed in claim 1, wherein said tin compound isbis(tri-n-butyltin)monochloromalate.

9. The method as claimed in claim 1, wherein said tin compound isbis(triphenyltin)monochloromalate.

10. The method as claimed in claim 1, wherein said tin compounds isbis(tri-n-butyltin)tetrachloroterephthalate.

11. The method as claimed in claim 1, wherein said tin compound isapplied to ships bottom and structures under sea water in combinationwith a coating film forming material selected from the group consistingof boiled oil, solvent naphtha, chlorinated rubber and barium sulfate.

- 6 References Cited UNITED STATES PATENTS 3,542,824 11/1970 Bublitz424-28-8 X 3,211,680 10/1965 Updegraff et al. 106-45 AF X 3,236,7932/1966 Robins et al. l06-15 AF X 3,214,453 10/1965 Stern, Jr 10615 AF X3,479,380 11/1969 Minieri 260--429.7

FOREIGN PATENTS 4,021,799 9/1965 Japan 260429.7

ALLAN LIEBERMAN, Primary Examiner R. ZAITLEN, Assistant Examiner US. Cl.X.R.

